43 キラルシクロペンタジエノンシントンの新合成と天然物合成への活用(口頭発表の部)

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概要

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• We found that the Lewis acid-mediated Diels-Alder reaction between cyclopentadiene and 4-tert-butoxy-2-cyclopentenone (±)-2 proceed stereoselectively in a contra-steric manner to give the endoalkoxy adduct (±)-3 in 92% yield. Based on this finding, a new and efficient preparation of optically pure ketodicyclopentadiene (KDP) (1) has been developed. Namely, racemic endo-alcohol (±)-5, generated from the contra-steric adduct (±)-3 by stereoselective reduction, afforded the optically pure acetate (-)-6 quantitatively leaving the optically pure alcohol (-)-5 in an excellent recovery when treated it with vinyl acetate in tert-butyl methyl ether in the presence of a lipase. Similarly, the racemic alcohol (±)-10 generated from racemic KDP (±)-1 gave the optically pure acetate (-)-11 and the optically pure alcohol (+)-10 in excellent yields. The contra-steric adduct (±)-3 also allowed the synthesis of the meso-diol 8 by sequential dealkylation and stereoselective reduction. The all resolved products were efficiently converted into optically pure KDP (1). Efficient preparation of optical pure KDP (1) as well as of the optically pure (β-alkoxy ketone 3 made more extensive utilization of these chiral buildings for the enantio- and diastereo-selective construction of natural products possible. Thus, new routes to the key dihydroxyaminocyclopentene segment 19 of Q nucleoside queuosine (12), the marine anthelmintic kainic acid (30), the marine triquinane sesquiterpene Δ^<9(12)>-capnellene (38), prostaglandin precursor 43, a potential precursor of the polyketide from wood-decay fungus sistodiolynne (47), and the estrogenic steroid estrone (56), have been established. Principle of the synthesis is stereoselective modification of the enone moiety of the biased tricyclic framework and thermal regeneration of the cyclopentene double bond. Based on this principle, the construction of the target molecules were successfully carried out except Δ^<9(12)>-capnellene (38) where whole carbon framework of KDP (1) was used. Newly developed procedures were based on tandem sigmatropic reaction linked to the retro-Diels-Alder step which allowed efficient preparation of prostaglandin precursor 43 and enantioconvergent construction of kainic acid (3). Another noteworthy was the stability of the β-alkoxyketone 3 under strong basic conditions which led to an enantioconvergent route to estrone (56).

• 天然有機化合物討論会の論文
• 1996-09-02

著者

• 小笠原 國郎

  東北大薬

• 菅原 勉

  東北大院薬

• 中田 善久

  東北大薬

• 菅原 勉

  東北大薬

• 田中 圭悟

  東北大薬

• 畔柳 ゆかり

  東北大薬

• Sugahara T

  Pharmaceutical Institute Tohoku University

• Ogasawara Kunio

  Pharmaceutical Institute Tohoku University

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